CN102093314B - Energy-saving method in process of producing epichlorohydrin by acetate propylene ester method - Google Patents
Energy-saving method in process of producing epichlorohydrin by acetate propylene ester method Download PDFInfo
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- CN102093314B CN102093314B CN201010599353A CN201010599353A CN102093314B CN 102093314 B CN102093314 B CN 102093314B CN 201010599353 A CN201010599353 A CN 201010599353A CN 201010599353 A CN201010599353 A CN 201010599353A CN 102093314 B CN102093314 B CN 102093314B
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Abstract
The invention discloses an energy-saving method in the process of producing epichlorohydrin by an acetate propylene ester method. The energy-saving method comprises the following steps: arranging a condenser (c) between an azeotropy tower (a) and a saponification tower (d). In the method, because the pressure of the saponification tower is low enough, secondary steam generated by most heat of steam from the tower top of the azeotropy tower can be directly utilized, thereby greatly saving steam consumption and improving economic benefits.
Description
Technical field
The present invention relates to a kind of allyl acetate method and produce the power-economizing method of epoxy chloropropane process.
Background technology
Epoxy chloropropane (ECH) is a kind of important chemical material and synthetic intermediate, and main application is to be used to prepare epoxy resin, also is the main raw material of epoxy group(ing) and phenoxy resin, can also make glycerine and the high wet strength resin that is used for the paper industry.
Epoxy chloropropane (ECH) early than 1854 by Berthelot with salt s.t. glycerine, at first find during then with the alkali lye hydrolysis.Before and after the sixties in 20th century, for adapting to the demand of epoxy resin production development, it is that raw material is produced as main products that epoxy chloropropane begins with the propenyl chloride.At present, the working method of epoxy chloropropane mainly contains two kinds of propylene high-temperature chlorination and allyl acetate methods in the industry.The former succeeded in developing and was applied to suitability for industrialized production by U.S. Shell company in 1948 first, and the epoxy chloropropane on the our times more than 95% adopts this method to produce.The latter is by AS of the FSU and Japan is clear and electrician company succeeded in developing respectively the eighties in 20th century.
Allyl acetate method synthesizing epoxy chloropropane mainly comprises following a few step: allyl acetate is synthetic, vinylcarbinol (AAL) is produced, synthesizing dichloropropanol (DCH), saponification reaction, dichlorohydrine is refining, epoxy chloropropane is refining and some auxiliary workshop sections.
(1) allyl acetate is synthetic
Under the effect of palladium and promotor, in the presence of acetic acid, adopt acetoxylation to make propylene and oxygen react the generation allyl acetate at a certain temperature.
CH
2＝CHCH
2+1/2O
2+CH
3COOH→CH
2＝CHCH
2OCOCH
3+H
2O (1)
(2) vinylcarbinol is produced in hydrolysis
Allyl acetate generates vinylcarbinol through hydrolysis reaction.60～80 ℃ of temperature, pressure 0.1～1.0MPa
CH
2＝CHCH
2OCOCH
3+H
2O→CH
2＝CHCH
2OH+CH
3COOH (2)
(3) 0～10 ℃ of temperature, under pressure 0.1～0.3MPa condition, vinylcarbinol and chlorine generate dichlorohydrine through addition reaction.
CH
2＝CHCH
2OH+Cl
2→CH
2ClCHClCH
2OH (3)
(4) dichlorohydrine and calcium hydroxide generation saponification reaction generate epoxy chloropropane.
Compare with traditional high-temperature chlorination and to have following characteristics:
A) quality product is high and stable;
B) adopt the acetoxylation technology to improve product yield, the raw material consumption index obviously reduces;
C) avoided high-temperature chlorination, operational condition is gentle, steady, noncoking, and the production fault is few;
D) sewage flow rate is few.
Shortcoming is that technical process is longer, and energy consumption is higher, causes process cost higher, and economic benefit is not as high-temperature chlorination.
Produce in the technological process of epoxy chloropropane in existing allyl acetate method; The steam that contains most of water, allyl acetate and vinylcarbinol through the discharging of azeotrope column cat head has only a small amount of the comprehensive utilization; Other all carried out direct condensation with recirculated water, slatterned most energy like this; Saponification column contains salt such as lime carbonate, calcium chloride, calcium hydroxide, can only heat with open steam in order to prevent to stop up, and needs to consume a large amount of primary steams.The energy consumption of whole process flow has 20-40% to consume on the rectifying energy consumption of azeotrope column and saponification column, will produce very big economic benefit so these two towers are carried out energy saving optimizing.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, the power-economizing method that provides a kind of allyl acetate method to produce the epoxy chloropropane process improves the economic benefit that the allyl acetate method is produced epoxy chloropropane.
Technical scheme of the present invention is summarized as follows:
A kind of allyl acetate method is produced the power-economizing method in the epoxy chloropropane process, comprises the steps: between azeotrope column (a) and saponification column (d), to be provided with condensing surface (c); The stream thigh (1) that will come from allyl acetate workshop section feeds the middle and upper part of non-pressurized azeotrope column (a); The stream thigh (2) that comes from allyl acetate hydrolysis workshop section feeds the middle part of non-pressurized azeotrope column (a), and the stream thigh (3) that comes from the allyl acetate hydrolysis workshop section of another equipment feeds the middle and lower part of non-pressurized azeotrope column (a); The stream thigh 6 that comes from the phase splitter of allyl acetate hydrolysis workshop section feeds the top of non-pressurized azeotrope column (a); The stream thigh (7) that contains water and acetic acid from the extraction of azeotrope column (a) side line supplies the washing usefulness of front workshop section, contains the stream thigh (4) of acetic acid and water from the bottom extraction of azeotrope column (a) tower still; The vapour stream thigh (16) that contains water, allyl acetate, vinylcarbinol and lighter-than-air gas from the top extraction of azeotrope column (a) passes through distributing T-pipe; Wherein a plume thigh 5 leads to the reboiler of vinylcarbinol treating tower; Another strand feeds the top of said condensing surface (c) as the hot-fluid thigh, and 75-95 ℃ saturation water feeds as the cold flow thigh (8) of the condensing surface top from said condensing surface; Lead to the profit phase splitter from the effusive stream of said condenser strand (9); Come out from said condensing surface bottom 75-95 ℃ saturated vapor (17) feeds the bottom of said saponification column (d); The working pressure of adjustment saponification column (d) is to 10-30Kpa; To come from the stream thigh (10) of milk of lime workshop section of auxiliary workshop section, feed the top of the saponification column (d) of low pressure from the mixed flow thigh (11) of dichlorohydrine workshop section and milk of lime workshop section, from the stream thigh (14) of the refining workshop section of epoxy chloropropane lights column with from the stream thigh (15) of the refining workshop section of epoxy chloropropane heavies column; What obtain from saponification column (d) cat head is the stream thigh (13) that contains epoxy chloropropane, dichlorohydrine and water, and what obtain from saponification column (d) tower still is the stream thigh (12) that contains calcium chloride, lime carbonate, calcium hydroxide and water.
Second kind of allyl acetate method produced the power-economizing method in the epoxy chloropropane process, comprises the steps: between azeotrope column (a) and saponification column (d), to be provided with condensing surface (c); The stream thigh (1) that will come from allyl acetate workshop section feeds the middle and upper part of non-pressurized azeotrope column (a); The stream thigh (2) that comes from allyl acetate hydrolysis workshop section feeds the middle part of non-pressurized azeotrope column (a), and the stream thigh (3) that comes from the allyl acetate hydrolysis workshop section of another equipment feeds the middle and lower part of non-pressurized azeotrope column (a); The stream thigh 6 that comes from the phase splitter of allyl acetate hydrolysis workshop section feeds the top of non-pressurized azeotrope column (a); The stream thigh (7) that contains water and acetic acid from the extraction of azeotrope column (a) side line supplies the washing usefulness of front workshop section, contains the stream thigh (4) of acetic acid and water from the bottom extraction of azeotrope column (a) tower still; The vapour stream thigh (16) that contains water, allyl acetate, vinylcarbinol and lighter-than-air gas from the top extraction of azeotrope column (a) passes through distributing T-pipe; Wherein a plume thigh 5 leads to the reboiler of vinylcarbinol treating tower; Another strand feeds the top of said condensing surface (c) as the hot-fluid thigh, and 75-95 ℃ saturation water feeds as the cold flow thigh (8) of the condensing surface top from said condensing surface; Lead to the profit phase splitter from the effusive stream of said condenser strand (9); Come out from said condensing surface bottom 75-95 ℃ saturated vapor (17) feeds the bottom of said saponification column (d) through vapor jet pump (e); The working pressure of adjustment saponification column (d) is to 40-55Kpa; To come from the stream thigh (10) of milk of lime workshop section of auxiliary workshop section, feed the top of the saponification column (d) of low pressure from the mixed flow thigh (11) of dichlorohydrine workshop section and milk of lime workshop section, from the stream thigh (14) of the refining workshop section of epoxy chloropropane lights column with from the stream thigh (15) of the refining workshop section of epoxy chloropropane heavies column; What obtain from saponification column (d) cat head is the stream thigh (13) that contains epoxy chloropropane, dichlorohydrine and water, and what obtain from saponification column (d) tower still is the stream thigh (12) that contains calcium chloride, lime carbonate, calcium hydroxide and water.
First kind of embodiment of the present invention because the pressure of saponification column is enough low, utilizes the secondary steam of most of heat generation of azeotrope column overhead vapours directly to be utilized, and can save steam consumption greatly like this, increases economic efficiency; Second kind of embodiment of the present invention can be high at the pressure of saponification column, and the secondary steam that most of heat of azeotrope column overhead vapours produces can not directly be utilized; This moment is through utilizing vapor jet pump; Low pressure secondary steam with the highly compressed working steam comes stripping to produce makes discharging steam reach suitable pressure, can directly use saponification column; Thereby the saving energy consumption reduces process cost.Second kind of embodiment good operability, good springiness, suitable system is how! Above-mentioned two kinds of schemes can both reduce the energy consumption that the allyl acetate method is produced the epoxy chloropropane process in a large number, play the purpose of increasing economic efficiency.
Description of drawings
Fig. 1 is the synoptic diagram that a kind of allyl acetate method is produced first kind of embodiment of epoxy chloropropane process power-economizing method.
Fig. 2 is the synoptic diagram that second kind of allyl acetate method produced epoxy chloropropane process power-economizing method embodiment.
Embodiment
Below in conjunction with accompanying drawing the present invention is described further:
A kind of allyl acetate method is produced the power-economizing method in the epoxy chloropropane process, between azeotrope column a and saponification column d, is provided with condensing surface c; The stream thigh 1 that will come from allyl acetate workshop section feeds the middle and upper part of non-pressurized azeotrope column a; The stream thigh 2 that comes from allyl acetate hydrolysis workshop section feeds the middle part of non-pressurized azeotrope column a, and the stream thigh 3 that comes from the allyl acetate hydrolysis workshop section of another equipment feeds the middle and lower part of non-pressurized azeotrope column a; The stream thigh 6 that comes from the phase splitter of allyl acetate hydrolysis workshop section feeds the top of non-pressurized azeotrope column a; Contain the washing usefulness of the stream thigh 7 confession front workshop sections of water and acetic acid from the extraction of azeotrope column a side line, contain the stream thigh 4 of acetic acid and water from the bottom extraction of azeotrope column a tower still; The vapour stream thigh 16 that contains water, allyl acetate, vinylcarbinol and lighter-than-air gas from the top extraction of azeotrope column a passes through distributing T-pipe; Wherein a plume thigh 5 leads to the reboiler of vinylcarbinol treating tower; Another strand feeds the top of said condensing surface c as the hot-fluid thigh, and 75-95 ℃ saturation water feeds as the cold flow thigh 8 of the condensing surface top from said condensing surface; Lead to the profit phase splitter from the effusive stream thigh 9 of said condenser; Come out from said condensing surface bottom 75-95 ℃ saturated vapor 17 feeds the bottom of said saponification column d; The working pressure of adjustment saponification column d is to 10-30Kpa; To come from the stream thigh 10 of milk of lime workshop section of auxiliary workshop section, feed the top of the saponification column d of low pressure from the mixed flow thigh 11 of dichlorohydrine workshop section and milk of lime workshop section, from the stream thigh 14 of the refining workshop section of epoxy chloropropane lights column with from the stream thigh 15 of the refining workshop section of epoxy chloropropane heavies column; What obtain from saponification column d cat head is the stream thigh 13 that contains epoxy chloropropane, dichlorohydrine and water, and what obtain from saponification column d tower still is the stream thigh 12 that contains calcium chloride, lime carbonate, calcium hydroxide and water.
A kind of allyl acetate method is produced the power-economizing method in the epoxy chloropropane process, between azeotrope column a and saponification column d, is provided with condensing surface c; The stream thigh 1 that will come from allyl acetate workshop section feeds the middle and upper part of non-pressurized azeotrope column a; The stream thigh 2 that comes from allyl acetate hydrolysis workshop section feeds the middle part of non-pressurized azeotrope column a, and the stream thigh 3 that comes from the allyl acetate hydrolysis workshop section of another equipment feeds the middle and lower part of non-pressurized azeotrope column a; The stream thigh 6 that comes from the phase splitter of allyl acetate hydrolysis workshop section feeds the top of non-pressurized azeotrope column a; Contain the washing usefulness of the stream thigh 7 confession front workshop sections of water and acetic acid from the extraction of azeotrope column a side line, contain the stream thigh 4 of acetic acid and water from the bottom extraction of azeotrope column a tower still; The vapour stream thigh 16 that contains water, allyl acetate, vinylcarbinol and lighter-than-air gas from the top extraction of azeotrope column a passes through distributing T-pipe; Wherein a plume thigh 5 leads to the reboiler of vinylcarbinol treating tower; Another strand feeds the top of said condensing surface c as the hot-fluid thigh, and 75-95 ℃ saturation water feeds as the cold flow thigh 8 of the condensing surface top from said condensing surface; Lead to the profit phase splitter from the effusive stream thigh 9 of said condenser; 75-95 ℃ saturated vapor 17 comes out from said condensing surface bottom; Feed the bottom of said saponification column d through vapor jet pump e; The working pressure of adjustment saponification column d is to 40-55Kpa; To come from the stream thigh 10 of milk of lime workshop section of auxiliary workshop section, feed the top of the saponification column d of low pressure from the mixed flow thigh 11 of dichlorohydrine workshop section and milk of lime workshop section, from the stream thigh 14 of the refining workshop section of epoxy chloropropane lights column with from the stream thigh 15 of the refining workshop section of epoxy chloropropane heavies column; What obtain from saponification column d cat head is the stream thigh 13 that contains epoxy chloropropane, dichlorohydrine and water, and what obtain from saponification column (d) tower still is the stream thigh 12 that contains calcium chloride, lime carbonate, calcium hydroxide and water.
Below in conjunction with specific embodiment the present invention is further described.
Present embodiment is the energy expenditure situation when not taking conservation measures:
The stream thigh 1 that comes from allyl acetate workshop section; Flow is 23588.4kg/h, and temperature is 90 ℃, and pressure is the middle and upper part that 0.16MPa feeds non-pressurized azeotrope column a; The mass fraction of water is 29.4% in the stream thigh 1; Acetic acid 34.8%, allyl acetate 22.2%, vinylcarbinol 12.9% and some impurity and lighter-than-air gas; The stream thigh 2 that comes from allyl acetate hydrolysis workshop section, flow are 56.1kg/h, and temperature is 37 ℃, and pressure is the middle part that 0.20MPa feeds normal pressure azeotrope column a, and the massfraction of acetic acid is 100% in the stream thigh 2; Come from the allyl acetate hydrolysis workshop section stream thigh 3 of another equipment, flow is 1800.7kg/h, and temperature is 110 ℃, and pressure 0.20MPa feeds the middle and lower part of non-pressurized azeotrope column a, flows moisture 26.1% (massfraction) in the thigh 3, contains acetic acid 73.9% (massfraction); The stream thigh 6 that comes from allyl acetate hydrolysis workshop section phase splitter; Flow is 7124.8kg/h, 38 ℃ of temperature, and pressure is 0.13MPa; Feed the top of non-pressurized azeotrope column a, the mass fraction of water is 29% in the stream strands 6, allyl acetate is 45%, vinylcarbinol 25.4% and partial impurities.The working pressure of azeotrope column a is 0.13MPa; Number of theoretical plate is taken as 50,93.2 ℃ of overhead vapours temperature, and tower still temperature is 114.5 ℃; It is that the 38th theoretical stage side line produced quantity is 1980kg/h that the azeotrope column side is adopted the position; The washing usefulness of stream thigh 7 confession front workshop sections, the main composition of stream strands 7 is vinylcarbinols of acetic acid and 4.0% (massfraction) of the water, 52% (massfraction) of 44% (massfraction), from the stream thigh 4 of acetic acid and 33.3% (massfraction) water of azeotrope column a tower still bottom extraction 66.7% (massfraction); The energy consumption of tower still is 6062.15446KW, and amounting to steam consumption quantity is 10086.3kg/h.
Come from the unitary stream thigh 10 of milk of lime; Temperature is 60 ℃; Pressure position 0.1MPa; Feed the top of decompression saponification column, wherein moisture 81.9% (massfraction), contain calcium hydroxide 11.3% (massfraction), calcium chloride 3.8% (massfraction), lime carbonate 1.6% (massfraction) and small amount of impurities; The mixed flow thigh 11 that comes from dichlorohydrine workshop section and milk of lime workshop section; Flow is 24038.3kg/h; Temperature is 70 ℃; Pressure is 0.1MPa, feeds the top of decompression saponification column, wherein moisture 64% (massfraction), contain dichlorohydrine 22.61% (massfraction), contain calcium hydroxide be 7.71% (massfraction), calcium chloride 2.62% (massfraction), lime carbonate 1.1% (massfraction) remaining be hydrochloric acid and partial impurities; Come from the stream thigh 14 of the refining workshop section of epoxy chloropropane lights column, flow is 1128.6kg/h, 120 ℃ of temperature; Pressure is 0.05MPa; Feed the top of decompression saponification column, wherein contain dichlorohydrine 27.4% (massfraction), trichloropropanol 72.6% (massfraction); The stream thigh 15 that comes from the refining workshop section of epoxy chloropropane heavies column feeds the top of decompression saponification column, flow 361.405kg/h, and wherein moisture 91.3% (massfraction), epoxy chloropropane are 8.0% (massfraction) and small amount of impurities; Open steam stream plume amount is 9000kg/h; Pressure is the bottom that 0.3MPa feeds the saponification column d of low pressure, and saponification column d number of theoretical plate is 40, and what obtain from saponification column d cat head is the stream thigh 13 that contains epoxy chloropropane, dichlorohydrine and water; The cat head working pressure is 50Kpa, 78.2 ℃ of tower top temperatures; What obtain from saponification column (d) tower still is the stream thigh 12 that contains calcium chloride, lime carbonate, calcium hydroxide and water, about 91 ℃ of tower still temperature.Overhead vapours ECH concentration 32.1%, tower still dichlorohydrine trace.
To sum up: it is 9000+10086.3=19086.3kg/h=19.0863t/h that former technology consumes the steam total amount altogether.
Present embodiment is the scheme one in the power-economizing method:
A kind of allyl acetate method is produced the power-economizing method in the epoxy chloropropane process, between azeotrope column a and saponification column d, is provided with condensing surface c; The stream thigh 1 that comes from allyl acetate workshop section; Flow is 23588.4kg/h, and temperature is 90 ℃, and pressure is the middle and upper part that 0.16MPa feeds non-pressurized azeotrope column a; The mass fraction of water is 29.4% in the stream thigh 1; Acetic acid 34.8%, allyl acetate 22.2%, vinylcarbinol 12.9% and some impurity and lighter-than-air gas; The stream thigh 2 that comes from allyl acetate hydrolysis workshop section, flow are 56.1kg/h, and temperature is 37 ℃, and pressure is the middle part that 0.20MPa feeds normal pressure azeotrope column a, and the massfraction of acetic acid is 100% in the stream thigh 2; Come from the allyl acetate hydrolysis workshop section stream thigh 3 of another equipment, flow is 1800.7kg/h, and temperature is 110 ℃, and pressure 0.20MPa feeds the middle and lower part of non-pressurized azeotrope column a, flows moisture 26.1% (massfraction) in the thigh 3, contains acetic acid 73.9% (massfraction); The stream thigh 6 that comes from allyl acetate hydrolysis workshop section phase splitter; Flow is 7124.8kg/h, 38 ℃ of temperature, and pressure is 0.13MPa; Feed the top of non-pressurized azeotrope column a, the mass fraction of water is 29% in the stream strands 6, allyl acetate is 45%, vinylcarbinol 25.4% and partial impurities.The working pressure of azeotrope column a is 0.13MPa; Number of theoretical plate is taken as 50,93.2 ℃ of overhead vapours temperature, and tower still temperature is 114.5 ℃; It is that the 38th theoretical stage side line produced quantity is 1980kg/h that the azeotrope column side is adopted the position; The washing usefulness of stream thigh 7 confession front workshop sections, the main composition of stream strands 7 is vinylcarbinols of acetic acid and 4.0% (massfraction) of the water, 52% (massfraction) of 44% (massfraction), from the stream thigh 4 of acetic acid and 33.3% (massfraction) water of azeotrope column a tower still bottom extraction 66.7% (massfraction); The energy consumption of tower still is 6062.15446KW, and amounting to steam consumption quantity is 10086.3kg/h.
The vapour stream thigh 16 that contains water, allyl acetate, vinylcarbinol and lighter-than-air gas from the top extraction of azeotrope column a passes through distributing T-pipe; Wherein a plume thigh 5 leads to the reboiler of vinylcarbinol treating tower; Another strand feeds the top of said condensing surface c as the hot-fluid thigh, and 90 ℃ saturation water feeds as the cold flow thigh 8 of the condensing surface top from said condensing surface; Lead to the profit phase splitter from the effusive stream of said condenser strands 9,90 ℃ the saturated vapor 17 of coming out from said condensing surface bottom feeds the bottom of said saponification column d, and the working pressure of adjustment saponification column d is to 30Kpa.
If overhead vapours all condensation can be emitted heat 5485.8811KW; But wherein some carries out heat exchange will for follow-up vinylcarbinol product tower; Through adjusting wherein, there is part tolerance to feed condensing surface, the heat that promptly in condensing surface, can utilize is 3017.23KW; According to vapor temperature, can roughly confirm to produce at most 90 ℃ of steam 3960kg/h.。
In order to utilize the energy of this part, we have reduced the cat head pressure drop of saponification reaction tower to 30KPa, have reduced open steam consumption so on the one hand, the heat that can utilize first condensing surface to produce on the one hand.
Situation for saponification column d is following:
Come from the unitary stream thigh 10 of milk of lime; Temperature is 60 ℃; Pressure position 0.1MPa; Feed the top of decompression saponification column, wherein moisture 81.9% (massfraction), contain calcium hydroxide 11.3% (massfraction), calcium chloride 3.8% (massfraction), lime carbonate 1.6% (massfraction) and small amount of impurities; The mixed flow thigh 11 that comes from dichlorohydrine workshop section and milk of lime workshop section; Flow is 24038.3kg/h; Temperature is 70 ℃; Pressure is 0.1MPa, feeds the top of decompression saponification column, wherein moisture 64% (massfraction), contain dichlorohydrine 22.61% (massfraction), contain calcium hydroxide be 7.71% (massfraction), calcium chloride 2.62% (massfraction), lime carbonate 1.1% (massfraction) remaining be hydrochloric acid and partial impurities; Come from the stream thigh 14 of the refining workshop section of epoxy chloropropane lights column, flow is 1128.6kg/h, 120 ℃ of temperature; Pressure is 0.05MPa; Feed the top of decompression saponification column, wherein contain dichlorohydrine 27.4% (massfraction), trichloropropanol 72.6% (massfraction); The stream thigh 15 that comes from the refining workshop section of epoxy chloropropane heavies column, flow 361.405kg/h, wherein moisture 91.3% (massfraction), epoxy chloropropane are 8.0% (massfraction) and small amount of impurities; Open steam stream strand pressure is that 0.3MPa feeds the saponification column bottom; Decompression saponification column d number of theoretical plate is 40; What obtain from saponification column d cat head is the stream thigh 13 that contains epoxy chloropropane, dichlorohydrine and water, and the cat head working pressure is 30KPa, 67 ℃ of tower top temperatures; What obtain from saponification column (d) tower still is the stream thigh 12 that contains calcium chloride, lime carbonate, calcium hydroxide and water, about 82.4 ℃ of tower still temperature.Overhead vapours ECH concentration 35%, tower still dichlorohydrine trace.
So the open steam flow that saponification column need add is 7400-3960=3440kg/h, and guaranteeing to improve product purity under the condition that the tower still requires.
The quantity of steam that embodiment 2 consumes altogether is 3440+10086.3=13526.3kg/h=13.5263t/h,
A kind of allyl acetate method is produced the power-economizing method in the epoxy chloropropane process, between azeotrope column a and saponification column d, is provided with condensing surface c; The stream thigh 1 that comes from allyl acetate workshop section; Flow is 23588.4kg/h, and temperature is 90 ℃, and pressure is the middle and upper part that 0.16MPa feeds non-pressurized azeotrope column a; The mass fraction of water is 29.4% in the stream thigh 1; Acetic acid 34.8%, allyl acetate 22.2%, vinylcarbinol 12.9% and some impurity and lighter-than-air gas; The stream thigh 2 that comes from allyl acetate hydrolysis workshop section, flow are 56.1kg/h, and temperature is 37 ℃, and pressure is the middle part that 0.20MPa feeds normal pressure azeotrope column a, and the massfraction of acetic acid is 100% in the stream thigh 2; Come from the allyl acetate hydrolysis workshop section stream thigh 3 of another equipment, flow is 1800.7kg/h, and temperature is 110 ℃, and pressure 0.20MPa feeds the middle and lower part of non-pressurized azeotrope column a, flows moisture 26.1% (massfraction) in the thigh 3, contains acetic acid 73.9% (massfraction); The stream thigh 6 that comes from allyl acetate hydrolysis workshop section phase splitter; Flow is 7124.8kg/h, 38 ℃ of temperature, and pressure is 0.13MPa; Feed the top of non-pressurized azeotrope column a, the mass fraction of water is 29% in the stream strands 6, allyl acetate is 45%, vinylcarbinol 25.4% and partial impurities.The working pressure of azeotrope column a is 0.13MPa; Number of theoretical plate is taken as 50,93.2 ℃ of overhead vapours temperature, and tower still temperature is 114.5 ℃; It is that the 38th theoretical stage side line produced quantity is 1980kg/h that the azeotrope column side is adopted the position; The washing usefulness of stream thigh 7 confession front workshop sections, the main composition of stream strands 7 is vinylcarbinols of acetic acid and 4.0% (massfraction) of the water, 52% (massfraction) of 44% (massfraction), from the stream thigh 4 of acetic acid and 33.3% (massfraction) water of azeotrope column a tower still bottom extraction 66.7% (massfraction); The energy consumption of tower still is 6062.15446KW, and amounting to steam consumption quantity is 10086.3kg/h.
The vapour stream thigh 16 that contains water, allyl acetate, vinylcarbinol and lighter-than-air gas from the top extraction of azeotrope column a passes through distributing T-pipe; Wherein a plume thigh 5 leads to the reboiler of vinylcarbinol treating tower; Another strand feeds the top of said condensing surface c as the hot-fluid thigh, and 90 ℃ saturation water feeds as the cold flow thigh 8 of the condensing surface top from said condensing surface; Lead to the profit phase splitter from the effusive stream of said condenser strands 9,90 ℃ the saturated vapor 17 of coming out from said condensing surface bottom feeds the bottom of said saponification column d through vapor jet pump e, and the working pressure of adjustment saponification column d is to 45Kpa.
If overhead vapours all condensation can be emitted heat 5485.8811KW; But wherein some carries out heat exchange will for follow-up vinylcarbinol product tower; Through adjusting, wherein there is part tolerance to feed condensing surface, the heat that promptly in condensing surface, can utilize is 3017.23KW; According to vapor temperature, can confirm to produce at most 90 ℃ of steam 3960kg/h.
In order to utilize the energy of this part, we have reduced the cat head pressure drop of saponification reaction tower a little, and we adopt vapor jet pump time 45KPa, with a kind of HP steam as working steam, gas carry obtain 0.20MPa secondary steam as working steam.Can access the flow 5700kg/h of the high-pressure work steam that will use, pressure 0.5MPa through calculating us.
The situation last for saponification column is following:
Come from the unitary stream thigh 10 of milk of lime; Temperature is 60 ℃; Pressure position 0.1MPa; Feed the top of decompression saponification column, wherein moisture 81.9% (massfraction), contain calcium hydroxide 11.3% (massfraction), calcium chloride 3.8% (massfraction), lime carbonate 1.6% (massfraction) and small amount of impurities; The mixed flow thigh 11 that comes from dichlorohydrine workshop section and milk of lime workshop section; Flow is 24038.3kg/h; Temperature is 70 ℃; Pressure is 0.1MPa, feeds the top of decompression saponification column, wherein moisture 64% (massfraction), contain dichlorohydrine 22.61% (massfraction), contain calcium hydroxide be 7.71% (massfraction), calcium chloride 2.62% (massfraction), lime carbonate 1.1% (massfraction) remaining be hydrochloric acid and partial impurities; Come from the stream thigh 14 of the refining workshop section of epoxy chloropropane lights column, flow is 1128.6kg/h, 120 ℃ of temperature; Pressure is 0.05MPa; Feed the top of decompression saponification column, wherein contain dichlorohydrine 27.4% (massfraction), trichloropropanol 72.6% (massfraction); The stream thigh 15 that comes from the refining workshop section of epoxy chloropropane heavies column, flow 361.405kg/h, wherein moisture 91.3% (massfraction), epoxy chloropropane are 8.0% (massfraction) and small amount of impurities; Open steam stream strand pressure is that 0.3MPa feeds the saponification column bottom, and decompression saponification column d number of theoretical plate is 40, and what obtain from saponification column d cat head is the stream thigh 13 that contains epoxy chloropropane, dichlorohydrine and water, and the cat head working pressure is 45KPa, 76 ℃ of tower top temperatures; What obtain from saponification column (d) tower still is the stream thigh 12 that contains calcium chloride, lime carbonate, calcium hydroxide and water, about 88 ℃ of tower still temperature.Overhead vapours ECH concentration 34%, tower still dichlorohydrine trace.The quantity of steam used of saponification column is exactly a vapor jet pump working steam consumption in this case:
So embodiment 3, consuming energy is 5700+10086.3=15786.3kg/h=15.7863t/h;
Also have the secondary steam that is not extracted of about 1600kg/h can be in addition as other workshop sections of technology as heat energy.
If adopt multi-stage jet, the working steam that then requires to use reduces, and the LP steam that the azeotrope column cat head produces can all utilize, and the energy that save this moment is: (19.0863-14.1863)/and 19.0863=25.67%.
Adopt unit injection and multi-stage jet all in the protection domain of this patent.
To sum up: when utilizing the cat head afterheat steam, can play the effect of good saving energy consumption through the pressure of adjustment saponification column.
Claims (2)
1. an allyl acetate method is produced the power-economizing method in the epoxy chloropropane process, it is characterized in that comprising the steps: between azeotrope column (a) and saponification column (d), being provided with condensing surface (c); The stream thigh (1) that will come from allyl acetate workshop section feeds the middle and upper part of non-pressurized azeotrope column (a); The stream thigh (2) that comes from allyl acetate hydrolysis workshop section feeds the middle part of non-pressurized azeotrope column (a), and the stream thigh (3) that comes from the allyl acetate hydrolysis workshop section of another equipment feeds the middle and lower part of non-pressurized azeotrope column (a); The stream thigh (6) that comes from the phase splitter of allyl acetate hydrolysis workshop section feeds the top of non-pressurized azeotrope column (a); The stream thigh (7) that contains water and acetic acid from the extraction of azeotrope column (a) side line supplies the washing usefulness of front workshop section, contains the stream thigh (4) of acetic acid and water from the bottom extraction of azeotrope column (a) tower still; The vapour stream thigh (16) that contains water, allyl acetate, vinylcarbinol and lighter-than-air gas from the top extraction of azeotrope column (a) passes through distributing T-pipe; Wherein a plume thigh (5) leads to the reboiler of vinylcarbinol treating tower; Another strand feeds the top of said condensing surface (c) as the hot-fluid thigh, and 75-95 ℃ saturation water feeds as the cold flow thigh (8) of the condensing surface top from said condensing surface; Lead to the profit phase splitter from the effusive stream of said condenser strand (9); Come out from said condensing surface bottom 75-95 ℃ saturated vapor (17) feeds the bottom of said saponification column (d); The working pressure of adjustment saponification column (d) is to 10-30Kpa; To come from the stream thigh (10) of milk of lime workshop section of auxiliary workshop section, feed the top of the saponification column (d) of low pressure from the mixed flow thigh (11) of dichlorohydrine workshop section and milk of lime workshop section, from the stream thigh (14) of the refining workshop section of epoxy chloropropane lights column with from the stream thigh (15) of the refining workshop section of epoxy chloropropane heavies column; What obtain from saponification column (d) cat head is the stream thigh (13) that contains epoxy chloropropane, dichlorohydrine and water, and what obtain from saponification column (d) tower still is the stream thigh (12) that contains calcium chloride, lime carbonate, calcium hydroxide and water.
2. an allyl acetate method is produced the power-economizing method in the epoxy chloropropane process, it is characterized in that comprising the steps: between azeotrope column (a) and saponification column (d), being provided with condensing surface (c); The stream thigh (1) that will come from allyl acetate workshop section feeds the middle and upper part of non-pressurized azeotrope column (a); The stream thigh (2) that comes from allyl acetate hydrolysis workshop section feeds the middle part of non-pressurized azeotrope column (a), and the stream thigh (3) that comes from the allyl acetate hydrolysis workshop section of another equipment feeds the middle and lower part of non-pressurized azeotrope column (a); The stream thigh (6) that comes from the phase splitter of allyl acetate hydrolysis workshop section feeds the top of non-pressurized azeotrope column (a); The stream thigh (7) that contains water and acetic acid from the extraction of azeotrope column (a) side line supplies the washing usefulness of front workshop section, contains the stream thigh (4) of acetic acid and water from the bottom extraction of azeotrope column (a) tower still; The vapour stream thigh (16) that contains water, allyl acetate, vinylcarbinol and lighter-than-air gas from the top extraction of azeotrope column (a) passes through distributing T-pipe; Wherein a plume thigh (5) leads to the reboiler of vinylcarbinol treating tower; Another strand feeds the top of said condensing surface (c) as the hot-fluid thigh, and 75-95 ℃ saturation water feeds as the cold flow thigh (8) of the condensing surface top from said condensing surface; Lead to the profit phase splitter from the effusive stream of said condenser strand (9); Come out from said condensing surface bottom 75-95 ℃ saturated vapor (17) feeds the bottom of said saponification column (d) through vapor jet pump (e); The working pressure of adjustment saponification column (d) is to 40-55Kpa; To come from the stream thigh (10) of milk of lime workshop section of auxiliary workshop section, feed the top of the saponification column (d) of low pressure from the mixed flow thigh (11) of dichlorohydrine workshop section and milk of lime workshop section, from the stream thigh (14) of the refining workshop section of epoxy chloropropane lights column with from the stream thigh (15) of the refining workshop section of epoxy chloropropane heavies column; What obtain from saponification column (d) cat head is the stream thigh (13) that contains epoxy chloropropane, dichlorohydrine and water, and what obtain from saponification column (d) tower still is the stream thigh (12) that contains calcium chloride, lime carbonate, calcium hydroxide and water.
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